CN103328546B - Polyamide having nanoparticles on the surface - Google Patents

Polyamide having nanoparticles on the surface Download PDF

Info

Publication number
CN103328546B
CN103328546B CN201180065631.6A CN201180065631A CN103328546B CN 103328546 B CN103328546 B CN 103328546B CN 201180065631 A CN201180065631 A CN 201180065631A CN 103328546 B CN103328546 B CN 103328546B
Authority
CN
China
Prior art keywords
polymkeric substance
particle
dispersion
weight
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180065631.6A
Other languages
Chinese (zh)
Other versions
CN103328546A (en
Inventor
S·杰恩
S·N·基拉潘戴尔拉马莫尔蒂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Advanced Chemicals Co Ltd
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN103328546A publication Critical patent/CN103328546A/en
Application granted granted Critical
Publication of CN103328546B publication Critical patent/CN103328546B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a method for producing polymer mixtures containing at least one polymer (A) and at least one component (B), comprising the following steps: (a) preparing (A) as a granulate;(b) preparing (B) as a liquid solution and/or dispersion in a dispersion medium; (c) applying the solution and/or dispersion prepared in step (b) in the form of drops by means of an atomiser to the granulate (A) prepared in step (a); (d) drying the granulate obtained in step (c); and (e) optionally carrying out one or more moulding steps.

Description

There is the polymeric amide of nano particle from the teeth outwards
Patent application claims enjoys the rights and interests of the U.S. Provisional Patent Application sequence number 61/416,319 in the application of application on November 23rd, 2010, and its full content is incorporated herein for reference.
The present invention relates to a kind of production and comprise at least one polymkeric substance and the method comprising the polymeric blends of other component of at least one, wherein the solution of other component described or liquid dispersion are applied on granular polymkeric substance by spraying gun, subsequently that polymer beads is dry, and usually process further in manufacturing process.
The form that wherein polymkeric substance uses is not pure material form usually, and is actually the form mixed with other component.Can the example of problem that often runs into of the polymkeric substance of thermoplasticity processing be wish that the polymkeric substance with high molecular is to obtain good mechanical property on the one hand, but there is low-molecular-weight polymkeric substance be easier to processing; But the mechanical property of products therefrom is then poor.
As described in WO2004/74360A and WO2008/084021A, a kind of method solving this problem becomes and mechanical property for using nano particle to improve stream.
But, it is difficult for being mixed by nano particle in polymkeric substance and making nano particle dispersed in polymeric substrates, because nano particle and polymkeric substance are at melt, as the mixing in forcing machine or melt mixer often causes nanoparticle aggregate to produce larger aggregate in mixing process, and the Beneficial Effect of nano particle is caused to reduce.
Another mode improving workability is for add hyperbranched polymer in thermoplastic polymer.Which improve mobility, especially long-term behaviour, for example, see WO2010/054933, WO2009/115535 and WO2009/115536.
When using organic compound, between mixing period, the thermal destruction of described compound is a problem, and volatile gases of in fact usually may overflowing.Thermal destruction decreases the amount of active compound in polymkeric substance, and in addition, if such as say that hydrolysis products is corrosive, then degraded product is to polymkeric substance, is harmful to desired application and/or to process systems used.
The object of the invention is for providing a kind of method of producing the polymeric blends with other component of at least one, the method avoids the stress produced owing to promoting the comparatively high temps of undesirable DeR simultaneously, and do not damage the dispersion of component of mixture, as more uneven in made dispersion.The method is especially intended to the production of the polymeric blends allowing to have nano particle, and wherein nano particle has maximum dispersion fineness and the formation of aggregates of nanoparticles minimizes.
The present invention realizes described object via producing containing at least one polymkeric substance (A) with containing the following methods of the polymeric blends of at least one component (B), said method comprising the steps of:
A () provides (A) of a granular form,
B () provides (B) of the dispersion in liquor and/or in dispersion medium,
C the drop of the solution provided in step (b) and/or dispersion, by spraying gun, is applied on the particle provided in step (a) by (),
D particle drying that () will obtain in step (c), and
E () optionally carries out one or more forming step.
Described at least one is that other component (B) applying on the polymer particles of small droplets form and the removal of dispersion medium subsequently obtain component (B) on the polymer particles evenly and very fine and closely woven dispersion, and does not need to make polymkeric substance and component (B) be exposed to thermal stresses.When polymkeric substance is used as component (B), as an example, it has obvious Beneficial Effect alleviating in the polymericular weight reduction during usually occurring in melt-mixing.When by the inventive method by nano particle and mixed with polymers time; the gathering of nano particle obviously reduces; this is as produced respectively by melt-mixing, produce in the present invention and the polymer-nanoparticle mixture extruded subsequently in each case relatively shown in.
When the polymkeric substance that described at least one is used as (A) is selected from the polymkeric substance produced via known solid state condensation, the inventive method especially can easily whole enter in production method, especially in condensation polymerization step, wherein the polymkeric substance of precondensation is preserved for some time under lower than the second-order transition temperature of polymkeric substance and the temperature of fusing point, to increase the molecular weight of polymkeric substance via further condensation reaction.
The present invention will be described in more detail below.
In the step (a) of the inventive method, at least one polymkeric substance (A) provides in granular form.Therefore, described at least one polymkeric substance (A) is in particle form.Measure by method of sieving, the D of particle 50value is generally 5 μm to 5mm, and preferably 50 μm to 4mm, and particularly preferably 100 μm to 2mm.In the present invention, particle diameter is the longest dimension of particle.Particle can any desired shape use in the present invention, and as circular, oval, cylindrical etc., and they can have regular or irregularly shaped and regular or irregular surface.
In the present invention, described at least one polymkeric substance (A) is preferably selected from thermoplastic polymer.For the present invention, " thermoplastic polymer " also referred to as thermoplastics be can thermoplasticity processing polymkeric substance, can via heating plastic distortion polymkeric substance.Herein thermoplastic polymer feature for they can via heating repeat viscous deformation.In the present invention, term thermoplastic polymer also cover thermoplastic elastomer.In principle, the inventive method can use the thermoplastics of any type.The list of suitable thermoplastics can at Kunststoff-Taschenbuch [Plastics Handbook], and ed.Saechtling, finds in 1989.The method of producing described thermoplastics is well-known, and many thermoplasticss are commercially available.The example of suitable thermoplastics is polymeric amide, polyester, as polybutylene terephthalate and polyethylene terephthalate, urethane, polycarbonate, and vinylaromatic polymer, as polystyrene, and multipolymer and composition thereof.
The present invention particularly preferably is, and described at least one polymkeric substance (A) is selected from the polymkeric substance can produced by polycondensation.They are also referred to as polycondensate.Polycondensation refers to via repetition condensation step and eliminates simple, and namely low-molecular-weight compound is as the polymerization of water.In polycondensate, polymeric amide, polyester and polycarbonate are the most frequently used.Some high-performance polymer also produces via polycondensation, and wherein example is polyetherketone, polyether-ether-ketone, PAEK, pi, polysulfones, polyethersulfone, PPSU and polyphenylene sulfide.
Other suitable polymkeric substance is polyolefine, as Natene and multipolymer, and/or homopolymer polypropylene or multipolymer, polyvinyl chloride, poly-(methyl) acrylate and this section and above listed by the mixture of thermoplastic polymer.
The preferred thermoplastic polymer of part is described hereinafter in more detail.
1. polymeric amide
According to ISO307, at 25 DEG C, measure in 0.5 % by weight polymkeric substance (in 96% sulfuric acid) solution, for the intrinsic viscosity (limiting viscosity of the polymeric amide of the inventive method, Staudinger (Staudinger) index in the past) be generally 90-350ml/g, preferred 110-240ml/g.
Preferred use molar weight M wfor hypocrystalline or the amorphous polymer of at least 5000g/mol, wherein they are described in US2 as an example, and 071,250, US2,071.251, US2,130,523, US2,130,948, US2,241,322, US2,312,966, US2,512,606 and US3,393, in 210.
These documents such as describe the polymeric amide produced by the lactam nucleus of 7-13 unit, as polycaprolactam, poly capryllactam and polylauryllactam, and also describe the polymeric amide obtained by the reaction of dicarboxylic acid and diamines.
The example of spendable dicarboxylic acid for having 6-12 carbon atom, the alkane dicarboxylic acid of a preferred 6-10 carbon atom and aromatic dicarboxylic acid.Wherein they are hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, terephthalic acid and/or m-phthalic acid.
Specially suitable diamines is for having 6-12 carbon atom, the alkane diamine of a preferred 6-8 carbon atom, and m-xylene diamine, two (4-aminophenyl) methane, two (4-aminocyclohexyl) methane, 2,2-bis-(4-aminophenyl) propane or 2,2-bis-(4-aminocyclohexyl) propane.
Preferred polymeric amide is polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and nylon-6/6,6, especially there is the hexanolactam unit of 5-95 % by weight content.Particularly preferably polycaprolactam (polymeric amide-6 or nylon-6) and polyhexamethylene adipamide (polymeric amide-6,6 or nylon-6,6).
These compounds such as can trade mark b and a is buied by BASF SE.
Also should mention such as can via the condensation at elevated temperature of 1,4-Diaminobutane and hexanodioic acid and the polymeric amide (nylon-4,6) obtained.The production method with the polymeric amide of this structure is such as described in EP38094A, EP38582A and EP39524A.Other suitable polymeric amide can obtain via the copolymerization of two or more monomers referred to above.The mixture exceeding a kind of polymeric amide is suitable equally, and blending ratio can regulate as required herein.
Other polymeric amide with special advantage is half aromatic copolyamides, and as nylon-6,6T and nylon-6,6/6, T, wherein they have and are less than 0.5 % by weight triamine content based on molecular weight, are preferably less than 0.3 % by weight (EP299444A).Half aromatic copolyamides with low triamine content can be produced via the method be described in EP129195A and EP129196A.
Other suitable polymeric amide comprises based on nylon-6, and 6, containing the uncoloured polymeric amide of suitable stablizer as amine.These compounds are passable aE product is obtained by BASF SE.Polymeric amide suitable is equally the mixture of the glass fiber reinforcement based on nylon-6.This series products is passable bE is buied by BASF SE.
2. polyester
Normally used polyester is based on aromatic dicarboxylate and aliphatic series and/or those of aromatic dihydroxy compound.
First group of preferred polyester is polyalkylene terephthalates, and wherein their alcohol structure division has 2-10 carbon atom.
This kind of polyalkylene terephthalates is that itself is known.Their main chain comprises the aromatic ring derived from aromatic dicarboxylic acid.Aromatic cycles as can by halogen, as chlorine or bromine, or by C 1-C 4alkyl, as methyl, ethyl, sec.-propyl or n-propyl or n-, the exclusive OR tertiary butyl replace.
These polyalkylene terephthalates can via aromatic dicarboxylic acid or its ester or ester forms derivative and aliphatic dihydroxy compound reacts in a known way and obtains.
Preferred dicarboxylic acid is NDA, terephthalic acid and m-phthalic acid or its mixture.32 % by mole at the most, preferably more than 10 % by mole of aromatic dicarboxylic acids can by aliphatic series or alicyclic dicarboxylic acid, as hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid and cyclohexane cyclohexanedimethanodibasic replace.% by mole data are based on the total molecular weight of polymkeric substance.
Preferred aliphatic dihydroxy compound is the glycol with 2-8 carbon atom, especially 1，2-ethandiol, 1, ammediol, BDO, 1,6-hexylene glycol, 1,4-hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1,4 cyclohexane dimethanol and neopentyl glycol or its mixture.
Particularly preferred polyester is the polyalkylene terephthalates obtained by the alkanediol with 2-6 carbon atom.Wherein, particularly preferably polyethylene terephthalate, Poly(Trimethylene Terephthalate) and polybutylene terephthalate and composition thereof.Same preferably PET (polyethylene terephthalate) and/or PBT (polybutylene terephthalate), it comprises at the most 1 % by weight, preferred 0.75 % by weight 1,6-hexylene glycol and/or 2-methyl isophthalic acid at the most, 5-pentanediol is as other monomeric unit.Weight percentage is based on the gross weight of polyalkylene terephthalates.
According to ISO1628, at 25 DEG C, be measure in 0.5 % by weight solution in the mixture be made up of phenol and orthodichlorobenzene of 1:1 at polyester in weight ratio, the intrinsic viscosity of polyester is generally 50-220, preferred 80-160.
Particularly preferably wherein end carboxyl group content is 100meq/kg polyester at the most, preferably 50meq/kg polyester, the especially at the most polyester of 40meq/kg polyester at the most.This kind polyester is such as produced by the method for DE4401055A.The content of terminal carboxyl(group) usually via volumetry, as measured by potentiometry.
The composition being suitable for the inventive method also comprises the polyester different from PBT, as the mixture of polyethylene terephthalate (PET) and/or polycarbonate.Such as, polyethylene terephthalate and/or polycarbonate ratio is in the mixture preferably at the most 50 % by weight, especially 10-30 % by weight based on the gross weight of 100 % by weight (A) herein.
The polyester being applicable to the inventive method also comprises biodegradable polyester, as the random aliphatic aromatic copolyester such as based on hexanodioic acid, succsinic acid, sebacic acid, BDO and 1,3 butylene glycol.These products are biodegradable, and monomer whose also can be obtained by renewable resources.Biodegradable polyester such as can trade mark obtained by BASF SE.
Use recycled material be also favourable, wherein example is PET, optionally with other polyalkylene terephthalates, as the mixture of PBT.
Recycled material can granular form or use with the form of ground material.Polyester stands the hydrolytic rupture caused by traces of moisture in the course of processing, and therefore can advise recycled material predrying.After dry, residual moisture content is preferably 0.01-0.7% based on polyester gross weight, especially 0.2-0.6%.
Another organizes the polyester that suitable polyester is the Wholly aromatic produced by aromatic dicarboxylic acid and aromatic dihydroxy compound.
Suitable aromatic dicarboxylic acid is the compound for the production of polyalkylene terephthalates listed above.Be preferably based on mixture to use by 5-100 % by mole of m-phthalic acid and 0-95 % by mole of terephthalic acid, especially the mixture of 50-80 % by mole of terephthalic acid and 20-50% m-phthalic acid formation.
3. polycarbonate
Described at least one polymkeric substance (A) used can comprise homo-polycarbonate or Copolycarbonate.Preferred use all poly-of dihydroxyphenyl propane and Copolycarbonate.Suitable polycarbonate can in a known way, and as via by the compound based on total amount 0.05-2.0 % by mole of bis-phenol at least trifunctional, the compound as having three or more phenols OH bases mixes and branching.
The molar weight M of optimization polycarbonate w(mass average value) is 10000-200000g/mol, preferred 20000-80000g/mol.
Polycarbonate such as can via bis-phenol and phosgene in interface, or the reaction (being known as pyridine method) with phosgene in homogeneous phase and producing, and molecular weight can in a known way, obtain via using the chain terminator of appropriate amount in all cases.
The present invention is polymeric amide particularly preferably, especially nylon-6, and 6 and nylon-6.These polymeric amide such as can trade mark commercial by BASF SE.The same preferred polyester of the present invention, especially polybutylene terephthalate (PBT).This kind of PBT can trade mark obtained by BASF SE.Equally particularly preferably polycarbonate.Further preferred copolymer comprises polymeric amide, polyester and/or polycarbonate and composition thereof.Particularly preferably described at least one polymkeric substance (A) is selected from polymeric amide, polyester, polycarbonate, containing the multipolymer of polymeric amide, polyester and/or polycarbonate, and the mixture be made up of described homopolymer and/or multipolymer.
The polymeric blends produced by the inventive method comprises at least one polymkeric substance (A) described in 1-99.9 % by weight based on the gross weight of polymeric blends usually; preferred 5-99.9 % by weight, particularly preferably at least one polymkeric substance (A) described in 8-99.9 % by weight.One, two or more polymkeric substance can be used as (A).If two or more polymkeric substance are used as (A), step (a) can use the mixture be made up of the particle of two or more polymkeric substance, but also by such as extruding together via by material, producing and to be made up of two or more polymkeric substance and to comprise the composite grain of the mixture be made up of two or more polymkeric substance and start.Composite grain and the particle prepared by a kind of polymkeric substance also can together with use.
The content of other component of at least one described in polymeric blends (B) is 0.1-99 % by weight based on the gross weight of polymeric blends usually, preferred 0.1-95 % by weight, particularly preferably 0.1-92 % by weight.The amount of at least one polymkeric substance described in Inventive polymers mixture (A) is 1-99.9 % by weight based on the gross weight of polymeric blends usually, preferred 5-99.9 % by weight, particularly preferably 8-99.9 % by weight.
Concentration range referred to above comprises polymeric blends in narrower meaning and known to intermediate form herein, and wherein component (B) is with the much higher masterbatch that concentration provides in (A).
Polymeric blends comprises 50-99.9 % by weight at least one polymkeric substance (A) and 0.1-50 % by weight component (B) usually based on the gross weight of polymeric blends in each case, preferred 90-99.9 % by weight at least one polymkeric substance (A) and 0.1-10 % by weight component (B), and polymeric blends particularly preferably comprises 95-99.9 % by weight at least one polymkeric substance (A) and 0.1-5 % by weight component (B).
In principle, component used (B) can comprise can suitable form, as any compound of spraying with solution, colloid, dispersion, suspension or emulsion form and material.Wherein they are low-molecular-weight organic and mineral compound, the organic compound of higher molecular weight, as polymkeric substance, and the mineral compound of higher molecular weight, as silicon sol etc.In addition also organic and inorganic nanoparticles is applied by the inventive method.Organic nanometer granule is such as polymer latex, and inorganic nanoparticles such as can be the metal oxide of fine particle.
The present invention preferably selects the described at least one component (B) from nano particle and/or polymkeric substance.
Number average bead diameter (also referred to as the granularity) (D-of nano particle 50value) be generally 1-500nm, preferred 1-250nm, more preferably 1-100nm, particularly preferably 1-50nm, particularly preferably 1-20nm.Mean particle size and size-grade distribution can move staging or Electronic Speculum (TEM and/or SEM) mensuration via dynamic light scattering, ultracentrifuge (being particularly suitable for the median size measuring colloidal solution), field flow.The nano particle with narrow or wide size-grade distribution can be used herein.
The length (overall dimension of nano particle) of nano particle size and diameter (minimum size of nano particle) are than being preferably 1-50, preferred 1-20, particularly preferably 1-5, especially 1-3.
In principle, any material as nano particle that those skilled in the art are known can be used as other component of at least one (B).Wherein they are the nano particle of carbon containing, as soccerballene, and carbon nanotube and carbon black, metal and semimetallic oxide compound and oxide hydrate and metal and metallic sulfide.
The methodological principle of production nano particle is that those skilled in the art are known.Nano particle can, by physical mechanical method, use the top-down strategy of acquisition to be obtained by particulate, and the method be such as the production of metal and ceramic nanoparticles.Herein, particulate is such as pulverized via grinding in high energy ball mill or by reactivity grinding.Chemical physics production method is according to bottom-up strategy, and it optionally utilizes atom/molecule self-organization mechanism in a controlled manner, establishes more complicated structure from former sub or slave molecule.Wherein they are such as the sol-gel method of carrying out in the liquid phase, and hydrothermal method and the precipitator method, and the method for carrying out in the gas phase, as plasma method, flame hydrolysis and spray pyrolysis.What also there is wide region such as can the nano particle buied of colloidal solution (colloidal sol) form.
Producing the method for colloidal sol is that those skilled in the art are known and be such as described in Iler, Ralph K. " The Chemistry of Silica ", 4th chapter: " Colloidal Silica Concentrated Sols ", John Wiley & Sons, New York, 1979, ISBN:0-471-02404-X, in 331-343 page.
The sol-gel method of producing metal and/or semimetallic oxide compound and/or oxide hydrate is that those skilled in the art are known equally.This Sol-Gel-like method is such as described in the people such as Sanchez, and Chemistry of Materials2001, in 13,3061-3083.
The present invention preferably, nano particle is selected from metal and semimetallic oxide compound and oxide hydrate, the especially oxide compound and oxide hydrate and composition thereof of Si, Ti, Fe, Ba, Zr, Zn, Al, Ga, In, Sb, Bi, Cu, Ge, Hf, La, Li, Nb, Na, Ta, Y, Mo, V, Sn.Particularly preferably be, nano particle is selected from Si, Ti and Ba, especially the oxide compound of Si and oxide hydrate.
Polymkeric substance as other component of at least one (B) can provide in the form of a solution, but they also can be the form of nano particle, as produced by letex polymerization or micro-emulsion polymerization.A rear statement is especially applied to cross-linked polymer.The present invention preferably uses branching and/or hyperbranched polymer as other component of at least one (B).Further preferably, the polymkeric substance being used as (B) is selected from polymine, polyetheramine and composition thereof.
For the present invention, " hyperbranched " feature refers to that the degree of branching DB of related polymer is 10-98%, preferred 25-90%, particularly preferably 30-80%, wherein hyperbranched degree is defined as DB (%)=100 × (T+Z)/(T+Z+L), wherein T is the mean number of the monomeric unit of end keyed jointing, and Z is the mean number of monomeric unit forming branch point, and L is the mean number of the monomeric unit of macromole neutral line keyed jointing at each polymkeric substance.
For the present invention, particularly preferably use the hyperbranched polyethyleneimine, hyperbranched polyetheramine and composition thereof of high functionality as other component of at least one (B).
For the present invention, the hyperbranched polyethyleneimine of high functionality for also having average at least 3 except secondary and tertiary amino, preferably at least 6, the particularly preferably product of at least 10 ends or functional pendant groups, the wherein said second month in a season and uncle's amino form polymer backbone.Functional group is preferably primary amino.The number of end or functional pendant groups limits without undergoing any top in principle, but the product with much larger number functional group can have undesirable performance, as high viscosity or poor solvability.The hyperbranched polyethyleneimine of high functionality of the present invention preferably has and is no more than 500 ends or functional pendant groups, especially no more than 100 end groups or side base.
For the present invention, polymine is such as by Ullmann's Encyclopedia of Industrial Chemistry, " Aziridines ", electronic edition (on December 15th, 2006 publish article) WO-A94/12560 in method obtain homopolymer or multipolymer.
Homopolymer can preferably via ethyleneimine (aziridine) in the aqueous solution or organic solution, the polymerization under Lewis acid or other acid or the acidic compound of cracking exist and obtaining.This kind of homopolymer is the branched polymer usually comprising primary, secondary and tertiary amino with the ratio of about 30%:40%:30%.Amino distribution can be by 13c NMR spectrographic determination.
Comonomer used preferably includes the compound with at least two amido functional groups.The suitable comonomer that can mention such as have the Alkylenediamine of 2-10 carbon atom at alkylene moiety, wherein preferred quadrol and propylene diamine herein.Other suitable comonomer is diethylenetriamine, Triethylenetetramine (TETA), tetren, dipropylenetriamine, three propylidene triamines, two (hexa-methylene triamines), aminopropyl ethylene diamine and diaminopropyl ethylene diamine.
The mean mol (weight average) of polymine is generally 100-3000000g/mol, especially 800-2000000g/mol.
The weight average molar amount of the polymine that the catalyzed polymerization herein stung via nitrogen third obtains is generally 800-50000g/mol, especially 1000-30000g/mol.The polymine with higher molecular weight especially can via mentioned polymine and two functional group's alkylated compounds, as chloromethyloxirane or 1, the reaction of 2-ethylene dichloride, or as described in EP-A873371 and EP-A1177035, via the polymeric ultrafiltration by having wide molecular weight distribution, or obtain via being cross-linked.
Other material being suitable as component (B) is crosslinked polymine, wherein they can via polymine and two-or multi-functional linking agent reaction and obtain, wherein they have at least one halohydrin unit, glycidyl unit, ethylenimine unit or isocyanate units or a halogen atom as functional group.The example that can mention is two chloro alcohol ethers of Epicholorohydrin or the polyalkylene glycol with 2-100 ethylene oxide and/or propylene oxide unit, and compound listed in DE-A19931720 and US4144123.The method of producing crosslinked polymine especially by specification sheets mentioned above and EP-A895521 and EP-A25515 known.The mean mol of crosslinked polymine is usually more than 20000g/mol.
Other material that can be used as component (B) is the polymine of grafting, wherein any compound that can react with the amino of polymine or imino-can be used as grafting agent.The grafting agent and the method that are applicable to the polymine of production grafting such as find in EP-A675914.
Amidation polymkeric substance is similarly applicable polymine, and usually can via polymine and carboxylic acid or its ester or acid anhydride, the reaction of carboxylic acid amides or carboxylic acid halides and obtaining.Amidation polymkeric substance can subsequently with mentioned cross-linking agents, its crosslinking degree depends on the content of amidation nitrogen-atoms in polymine chain.Preferably 30% amido functional group is amidated at the most herein, still can obtain the uncle of sufficient amount and/or secondary nitrogen-atoms to make crosslinking reaction subsequently.
Oxyalkylated polymine is also suitable, and they such as can obtain via the reaction of polymine and ethylene oxide and/or propylene oxide and/or oxybutylene.Subsequently, this kind of Alkoxylated polymers crosslinkable again.
Be suitable as component (B) and other polymine that can mention is the polymine (mixing anion-radicals) of hydroxylated polymine and both sexes and the polymine of oleophylic, wherein they obtain via long chain hydrocarbon structure division is mixed polymer chain usually.The method of producing this kind of polymine is that those skilled in the art are known, and therefore, other details is thus unnecessary.
The weight average molar amount being used as the polymine of component (B) via determination of light scattering is preferably 800-50000g/mol, particularly preferably 1000-40000g/mol, especially 1200-30000g/mol.Mean mol (weight average), preferably by gel permeation chromatography, uses amylopectin as standard substance, at the aqueous solution (water; 0.02mol/l formic acid; 0.2mol/l KCl) middle mensuration.
Advantageously, according to DIN53176, the amine value as the polymine of component (B) is 50-1000mg KOH/g.According to DIN53176, the amine value as the polymine of component (B) is preferably 100-900mg KOH/g, very preferably 150-800mg KOH/g.
For the present invention, the hyperbranched polyetheramine of high functionality for also having average at least 3 except ether and amino, preferably at least 6, the particularly preferably polymkeric substance of at least 10 ends or functional pendant groups, wherein said ether and amino formation polymer backbone.Functional group is preferably OH base.The quantity of end or functional pendant groups does not limit by any top in principle, but the product with much larger number functional group can have undesirable performance, as high viscosity or poor solvability.The hyperbranched polyether amine polyol of high functionality of the present invention preferably has and is no more than 500 ends or functional pendant groups, especially no more than 100 end groups or side base.
Polyetheramine can obtain via following reaction:
-at least one has the tertiary amine of hydroxy functional group, especially at least one two-, three-or four alkanolamines,
Optional under the existence of following material:
-secondary amine, wherein they are with the hydroxyl of alternatively base, especially two alkanolamines,
And/or optional under the existence of following material:
-functionality is the polyether glycol of 2 or higher,
Wherein reaction is preferably carried out under ether exchange catalysts and catalyst for etherification exist.
In addition, preferred embodiment as the polymkeric substance of component (B) is reacted by making ethylene oxide and/or propylene oxide and/or oxybutylene and the polyetheramine that can obtain as mentioned above further and obtains, and they are especially having inner polyethylene oxide block and having the polymine of outside polyoxypropylene block as described in the european patent application as document reference number 07120395.4, and the oxyalkylated polymine as described in the european patent application of document reference number 07120393.9.
The preferred average per molecule of polyetheramine as component (B) has at least 3 OH functional groups, and namely OH average functionality is at least 3.Particularly preferably be, as component (B) polyetheramine can via at least one trialkanolamine optional with two alkanolamines and/or optional and functionality be 2 or higher Aethoxy Sklerol react and obtain.
After reaction, namely under not improving further, hyperbranched polyetheramine (B) has terminal hydroxyl.They have good solubility in all kinds of SOLVENTS.
The example of these solvents is aromatics and/or fat (ring) race hydrocarbon and composition thereof, and other example is halon, ketone, ester and ether.
The OH value favourable to the polyetheramine being used as component (B) according to DIN53240 mensuration is 50-1000mg KOH/g.According to DIN53240, the OH value of component (B) is preferably 100-900mg KOH/g, very preferably 150-800mg KOH/g.
As the weight average molar amount M of the polyetheramine of component (B) wbe mainly 1000-500000g/mol, preferred 2000-300000g/mol, and the equal molar weight M of number nbe mainly 500-50000g/mol, preferred 1000-40000g/mol, it is by gel permeation chromatography (GPC), uses hexafluoroisopropanol to measure as standard substance as mutually mobile and polymethylmethacrylate (PMMA).
In the step (b) of the inventive method, other component of described at least one (B) with liquor and/or in dispersion medium the form of dispersion provide.Dispersion medium is similarly liquid usually herein.
For the present invention, liquid refers to solution/dispersion or dispersion medium separately for flowable and can grind generation small droplets by selected spraying gun.For the present invention, dispersion is the multiphase mixture having at least one liquid phase and have at least one other liquid and/or solid-phase, and wherein example is emulsion and suspension.For the present invention, suspension is solid particulate dispersion in the liquid phase, the especially suspension of nano particle or granular polymer.In the present invention, emulsion is the multiphase mixture with at least two liquid phases.
Dispersion medium is selected from solvent and solvent mixture usually, as water, aliphatic C 1-C 6alcohol, optional alkylating aromatic hydrocarbon, fat (ring) race hydrocarbon, chain acid alkyl ester, ketone, oxyalkylated chain acid alkyl ester, halon and composition thereof.
Particularly preferably single-or polyalkylated benzene and naphthalene, ketone, chain acid alkyl ester and oxyalkylated chain acid alkyl ester and composition thereof.
Preferred aromatic hydrocarbon mixture comprises aromatics C for accounting for main advantage 7-C 14hydrocarbon and those of the boiling spread of 110-300 DEG C can be comprised, wherein particularly preferably toluene, o-, m-or p-Xylol, trimethylbenzene isomer, durene isomer, ethylbenzene, isopropyl benzene, naphthane and comprise their mixture.
Example is from ExxonMobil Chemical's herein product, particularly 100 (CAS No.64742-95-6 accounts for the C of main advantage 9-and C 10aromatic hydrocarbons, boiling spread is about 154-178 DEG C), 150 (boiling spread is about 182-207 DEG C) and 200 (CAS No.64742-94-5), and from Shell's product.Based on paraffinic hydrocarbon, naphthenic hydrocarbon and aromatic hydrocarbons hydrocarbon mixture also can crystal oil (as crystal oil 30, boiling spread is about 158-198 DEG C or crystal oil 60:CAS No.64742-82-1), petroleum solvent (same as CAS No.64747-82-1) or solvent naphtha (light: boiling spread is about 155-180 DEG C, weight: boiling spread is about 225-300 DEG C) buy.The aromaticity content of these hydrocarbon mixtures usually more than 90 % by weight, preferably greater than 95 % by weight, particularly preferably more than 98 % by weight, very particularly preferably more than 99 % by weight.Advantageously use the hydrocarbon mixture with the naphthalene content reduced especially.
The example of halon is chlorobenzene and dichlorobenzene and dichlorobenzene isomer mixture.
The example of ester is n-butyl acetate, ethyl acetate, 2-acetic acid 1-methoxy-propyl ester and acetic acid 2-methoxy ethyl ester.
The example of ether is THF, two alkane, and the dimethyl of ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol or tripropylene glycol, diethyl or di-n-butyl ether.
The example of ketone is acetone, 2-butanone, 2 pentanone, propione, hexanone, isobutyl methyl ketone, heptanone, cyclopentanone, pimelinketone and suberone.
The example of fat (ring) race hydrocarbon is the isomer mixture of naphthalane, alkylation naphthalane and straight chain or branched paraffin and/or cycloalkyne.
Further preferably n-butyl acetate, ethyl acetate, acetic acid 1-methoxyl group-2-propyl diester, acetic acid 2-methoxy ethyl ester, 2-butanone, isobutyl methyl ketone, and especially with the mixture of aromatic hydrocarbon listed above.
This kind of mixture can the volume ratio of 5:1-1:5, preferably with the volume ratio of 4:1-1:4, particularly preferably with the volume ratio of 3:1-1:3, very particularly preferably produces with the volume ratio of 2:1-1:2.
Preferred solvent be butylacetate, acetic acid methoxy-propyl ester, isobutyl methyl ketone, 2-butanone, product and dimethylbenzene.
The example being applicable to other solvent of polyetheramine is water, alcohol, as methyl alcohol, ethanol, butanols, and alcohol/water mixture, acetone, 2-butanone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N-ethyl pyrrolidone, ethylene carbonate and Texacar PC.
There is provided in step (b) and comprise the solution of other component of described at least one (B) and/or dispersion comprises other component of 1-50 % by weight at least one (B) based on the gross weight of solution/dispersion used usually for step (c); preferred 5-50 % by weight, particularly preferably 5-30 % by weight.Solution/dispersion can comprise one, two or more components (B).
In the step (c) of the inventive method, the solution of at least one component (B) and/or dispersion are applied on described at least one polymkeric substance of a granular form (A) with very thin drops.The described at least one component (B) be such as included in drop with form of nanoparticles at the surface of the particles, and is applied on particle with dispersed by the droplet deposition produced via atomization.Subsequently, usually via the preferred liquid dispersion medium of dispersion particle drying removed for generation of (B) and/or solution.Comprise the mixture of (A) and (B) further homogenizing can via subsequently be coated with (B) particle melt-mixing and realize.Therefore, polymer nano granules (mixture be made up of polymkeric substance and nano particle) especially can be produced under the nano particle of the gathering of obvious lower level, wherein they can have flow preferably change, machinery and thermal characteristics.
Spendable spraying gun is the known general-purpose equipment of those skilled in the art, as the single-fluid nozzles that pressurizes, wherein there is turbulization and form the nozzle of jet (hydraulic atomizer) and form the laminar nozzle with dual-flow atomizer (pneumatic atomizer), rotary atomizer and the ultrasonic atomizer that outside or inside mixes.The summary of the atomization technique that those skilled in the art are known such as can at Perry's Chemical Engineers'Handbook, and the 8th edition, 2008, eds.D.W.Green and R.H.Perry, finds in 14-93 to 14-95 page.In the present invention, preferably using in step (c) and producing mean diameter is 0.5-100 μm, preferred 0.5-20 μm, particularly preferably the spraying gun of drop of 0.5-10 μm, and described diameter is calculated by the size-grade distribution by Dynamic Light Scattering Determination.As an example, the Spraytec equipment from Malvern can be used for carrying out described mensuration.
In step (c) of the present invention, preferably use ultrasonic atomizer, it is also known as ultrasonic mist generator.Ultrasonic atomizer is used for the field of unusual wide region, as be used as humidification mist generator or in order to medical object is for sucker.The ultrasound system being applicable to the inventive method such as by ultraschallsysteme GmbH, Neuenb ü rg (Germany) provides.In the present invention, ultrasonic atomizer is the device operated in 25kHz to 5MHz range of frequency.In the present invention, in preferred steps (c), ultrasonic atomizer operates in 750kHz to 3MHz range of frequency.This is also referred to as million sound (megasonic) range of frequency.
Preferably use the dispersion medium that surface tension is 35-100mN/m in the present invention, it measures at 25 DEG C.Same preferred viscosities is 0.1-500mPas, particularly preferably the dispersion medium of 1-100mPas, and it is measured at temperature namely prevailing between atomization period at service temperatures.
The example of suitable dispersion medium is the mixture of water and solvent and water, and its surface tension measured at 25 DEG C is 35-100mN/m.When using ultrasonic atomizer, the method is particularly preferred, because for the solution/dispersion of other component of described at least one (B), particularly advantageously uses herein and has the viscosity and capillary dispersion medium that are similar to water.
Step (c) can wherein on polymkeric substance of a granular form, can obtain to be produced by spraying gun and comprised in well distributed any device of the solution of (B) and/or the drop mist of suspension to carry out, and wherein example is tower.In the present invention preferably, in step (c), particle is fixed bed or fluidized-bed form.Fluidized-bed such as can produce by passing through of inert gas, and wherein it is applied in the particle of spraying simultaneously in step (c) for drying.
Step (c) can use comprise one, the solution of other component of at least one described in two or more (B) and/or dispersion, but also can use in step (c) and exceed a kind of solution/dispersion, and such as start by applying a kind of solution of other component (B) and/or dispersion, and subsequently the solution of other component of the second (B) and/or dispersion are applied on particle, by that analogy.
Usual continuation steps (c), until be applied to particle by the component (B) of aequum.This is cost 0.5-60 minute usually.
Temperature when step (c) is carried out preferably with for the production of the solution of (B) and/or the dispersion medium of dispersion is mated, and this means that liquid dispersion medium is easily removed under being intended to temperature prevailing in step (c), especially easily evaporate.
Step (c) of the present invention, preferably at least 10 DEG C, preferably at least 20 DEG C, is particularly preferably carried out at the temperature of at least 30 DEG C.
In step (d), by the particle drying obtained in step (c).In the present invention " drying " refer to by be applied to together with the solution of (B) and/or dispersion in step (c) on particle dispersion medium remove.This such as can by inert gas by realize.In the present invention, " rare gas element " refer to described at least one polymkeric substance (A) or with the nonreactive gaseous substance of described at least one component (B) or substance mixture.Depend on the selection of (A) and (B), can difference be there is herein.The example of suitable inert gas is N 2, He or Ar or other, as long as the resistance to oxygen of material, air.
The temperature of inert gas is preferably at least 20 DEG C, particularly preferably at least 100 DEG C herein.The temperature of inert gas used herein is the respective decomposition temperature lower than described at least one component (B) and at least one polymkeric substance (A) or second-order transition temperature or fusing point preferably.
Can step (e) be carried out after step (d), wherein optionally carry out one or more forming step.The forming step that can carry out is the known any method of those skilled in the art and other method, as melt-mixing, extrude, blowing, injection moulding etc.The polymeric blends produced by the inventive method also can be processed further together with other polymkeric substance, and they especially can be used as the known masterbatch for component (B) being introduced other polymkeric substance or polymeric blends.The polymeric blends produced by the inventive method can be used for producing the known goods from plastic working, as fiber, paper tinsel, work in-process and moulded product, if houseware, electronic component, medical treatment device, vehicle component, the box for electronic installation, the box for electronic component in motor vehicle, wheel hub are around (wheel surround), door-plate, rear deflector door, spoiler, intake manifold, water tank and the box for electronic tool.
The inventive method can be carried out continuously or in batches.
Embodiment is used to set forth the present invention hereinafter.
Embodiment 1: the polymeric amide (the present invention) with colloid silica
Will b27E (BASF SE, before extrusion, the polymeric amide according to ISO307 intrinsic viscosity IV=150) as polymeric amide.Calculate, by median size D according to the size-grade distribution by Dynamic Light Scattering Determination 50for 8nm silicon dioxide gel ( cC/360Eka Chemicals) as nano particle.
Be that the polyamide granules of 0.5-2nm is deposited in the fixed bed of little (laboratory-scale) by mean sizes.Under 1MHz frequency, by ultrasonic atomizer (there is the Sonosys million sound spraying gun of Slimline producer) by silicon dioxide gel (30 % by weight, in water) dispersion atomization, and make small droplet mist pass through fixed bed through 2-5 minute.Make nitrogen gas stream at 75 DEG C by fixed bed with dried particles simultaneously.Once atomising method terminates, then using particle in nitrogen gas stream dry 5 minutes and discharge as final product again.Subsequently in DSM icroextrusion machine (twin screw extruder), at 280 DEG C, with 250 revs/min, particle was extruded under 1 minute residence time.Measure for some, test sample is produced by injection moulding (injection temperature 280 DEG C).
Comparative example 1 (V1): the polymeric amide (non-invention) without nano SiO 2 particle
Polymeric amide (not having nano particle) from embodiment 1 is extruded under the same conditions as example 1 and processes and produce test sample.
Comparative example 2 (V2): the polymeric amide (non-invention) with the nano SiO 2 particle of 1 % by weight melt-mixing
By the polymeric amide from embodiment 1 and the colloidal silica dispersion from embodiment 1 under condition described in embodiment 1, mix in icroextrusion machine; Silicon dioxide gel heat is introduced.Production test sample as described in Example 1 subsequently.
The size-grade distribution of nano particle in polymeric substrates measures the polymeric blends from embodiment 1 and comparative example 2 each via electron microscopy (SEM, scanning electron microscope).Table 1 shows result.
Table 1:
Statistical function fundamental unit V2 (non-invention) Embodiment 1 (the present invention)
The nano particle number detected 1075 803
? Diameter [μm] Diameter [μm]
Mean value (number all) 2.37 0.49
Intermediate value 2.42 0.44
Minimum value 0.28 0.14
Maximum value 5.87 1.69
Standard deviation 0.99 0.28
Variance 0.98 0.08
Mean value (quality is average) 3.09 0.81
In the polymeric blends produced by the inventive method, nano particle is significantly less than the nano particle in the polymeric blends produced via nano particle and Mixing of Polymer Melt.Nano particle applying on the polymer particles in small droplet form significantly reduces the aggregation extent of the nano particle producing larger particles.
The test sample produced in embodiment 1, V1 and V2 is used for the tensile property measured according to ISO527-2 in tensile stress test.Young's modulus measures according to ISO527-2.Table 2 compares result.This table also show according to DIN53727, and with 0.5 % by weight solution in 96 % by weight sulfuric acid, the intrinsic viscosity (IV) of polymeric amide and according to ISO1133, uses the measurement result of the melt flow index (MVR) of 270 DEG C/5kg load.
Table 2:
Obviously, the break-draw that the polymeric blends produced in the present invention shows apparently higher than two comparative examples strains, and simultaneously compared with unfilled polymeric amide, does not in fact affect tensile strength herein.Melt flow index (MVR) also apparently higher than unmodified polymeric amide, and also apparently higher than the polymeric amide comprising the nano particle that melt adds.Therefore, the inventive method can be produced and be comprised nano particle and wherein nano particle exists with obviously less form, the polymeric blends that the aggregation extent of the nano particle namely produced during polymer production is less; In addition, these polymeric blends have the mechanical property of improvement and good processibility.
Embodiment 2a and 2b: the polymeric amide (the present invention) with polymine
Polymeric amide from embodiment 1 is dropped into chuck post.Temperature is about 170 DEG C, and is rinsed by this post hot nitrogen in whole experimentation.Ultrasonic atomizer be positioned at post middle part and under 1MHz frequency, by aequum (15.6g/h) in polymine (the molar weight M of solution form (10 % by weight, in water) w: 1300g/mol; PH11, the viscosity at 20 DEG C: 20000Pas, g20, BASF SE) be sprayed on polyamide granules.In continuous processing, 300g particle nitrogen per hour preheating 1 hour is added from the top of post.By this post and after applying polyethylenimine solution, from the particle (embodiment 2a) of bottom removing respective amount.
Subsequently at 206 DEG C, in DSM icroextrusion machine (twin screw extruder), with 250 revs/min, partial particulate was extruded (embodiment 2b) under 3 minute residence time.
As mentioned above, the sample from embodiment 2a and 2b is used for measuring melt flow index, and is determined at the intrinsic viscosity before and after melt flow index measurement.
Comparative example 3a and 3b (V3a-b): the polymeric amide (non-invention) without polymine
A part of polymeric amide is directly used in measurement (comparative example V3a)
At 206 DEG C, in DSM icroextrusion machine (twin screw extruder), with 250 revs/min, partial particulate was extruded (comparative example V3b) under 3 minute residence time.
As mentioned above, the sample from comparative example 3a and 3b is used for measuring melt flow index, and is determined at the intrinsic viscosity before and after melt flow index measurement.
Comparative example 4a and 4b (V4a-b): the polymeric amide (non-invention) with the polymine of melt-mixing
At 280 DEG C, under 2 minute residence time, used twin screw extruder by the polymeric amide from embodiment 1 and the polyethylenimine solution melt-mixing (comparative example V4a) from embodiment 2.
Subsequently at 206 DEG C, in DSM icroextrusion machine (twin screw extruder), with 250 revs/min, part was extruded (comparative example V4b) from the particle of comparative example 4a under 3 minute residence time.
As mentioned above, the sample from comparative example 4a and 4b is used for measuring melt flow index, and is determined at the intrinsic viscosity before and after melt flow index measurement.
Table 3 compares the measuring result of intrinsic viscosity from embodiment 2a-b and comparative example 3a-3b and 4a-4b and melt flow index.
Table 3:
The contrast of V3 and embodiment 2 shows, when the polymeric blends that the present invention produces, the amount of the degraded produced is less (higher IV) (V3b and 2b compares), or when degradation amount is identical, the melt flow index of the polymeric blends that the present invention produces is obviously higher, and therefore these mixtures have good thermoplastic processibility.If the polymeric blends with polymine produces via melt-mixing, then compared with the polymeric blends situation of producing with the present invention, create the degraded (lower IV) of obvious higher level.

Claims (16)

1. production comprises at least one polymkeric substance (A) and comprises a method for the polymeric blends of other component of at least one (B), and it comprises the following steps:
A () provides (A) of a granular form,
B () provides (B) of the dispersion in liquor and/or in dispersion medium,
C the drop of the solution provided in step (b) and/or dispersion, by spraying gun, is applied on the particle provided in step (a) by (),
D particle drying that () will obtain in step (c), and
E () optionally carries out one or more forming step,
Wherein described in step (c), particle is the form of fixed bed or fluidized-bed,
The mean diameter D of the drop wherein produced by spraying gun in step (c) 50for 0.5-10 μm.
2. method according to claim 1, wherein measures via method of sieving, the D of the particle provided in step (a) 50value be 5 μm to 5mm.
3., according to the method for claim 1 or 2, wherein ultrasonic atomizer is used as the spraying gun in step (c).
4. method according to claim 3, wherein in step (c), the range of frequency of ultrasonic atomizer operation is 25kHz to 5MHz.
5., according to the method for claim 1 or 2, wherein step (c) is carried out at the temperature of at least 10 DEG C.
6., according to the method for claim 1 or 2, wherein in step (d), described particle is dry by the process of inert gas.
7., according to the method for claim 1 or 2, wherein said at least one polymkeric substance (A) is selected from thermoplastic polymer.
8., according to the method for claim 1 or 2, wherein said at least one polymkeric substance (A) is selected from the polymkeric substance can produced by polycondensation.
9. according to the method for claim 1 or 2, wherein said at least one polymkeric substance (A) is selected from polymeric amide, polyester, polycarbonate, containing the multipolymer of polymeric amide, polyester and/or polycarbonate, and the mixture be made up of described homopolymer and/or multipolymer.
10., according to the method for claim 1 or 2, other component of wherein said at least one (B) is selected from nano particle and/or polymkeric substance.
11. methods according to claim 10, are wherein used as the D of the nano particle of (B) 50value is 1-500nm.
12. according to the method for claim 10 or 11, and the wherein said nano particle being used as (B) is selected from metal and semimetallic oxide compound and oxide hydrate.
13. methods according to claim 10, the wherein said polymkeric substance being used as (B) is selected from branching and hyperbranched polymer.
14. according to the method for claim 10 or 13, and the wherein said polymkeric substance being used as (B) is selected from polyetheramine, polymine, polycarbonate and composition thereof.
15. according to the method for claim 1 or 2, and be wherein selected from the mixture of water and solvent and water for the dispersion medium of (B), its surface tension measured at 25 DEG C is 35-100mN/m.
16. according to the method for claim 1 or 2, and it carries out continuously or in batches.
CN201180065631.6A 2010-11-23 2011-11-15 Polyamide having nanoparticles on the surface Active CN103328546B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10192240 2010-11-23
EP10192240.9 2010-11-23
PCT/EP2011/070184 WO2012069340A1 (en) 2010-11-23 2011-11-15 Polyamide having nanoparticles on the surface

Publications (2)

Publication Number Publication Date
CN103328546A CN103328546A (en) 2013-09-25
CN103328546B true CN103328546B (en) 2015-01-07

Family

ID=44936296

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180065631.6A Active CN103328546B (en) 2010-11-23 2011-11-15 Polyamide having nanoparticles on the surface

Country Status (8)

Country Link
EP (1) EP2643390B1 (en)
JP (1) JP5795075B2 (en)
KR (1) KR101905206B1 (en)
CN (1) CN103328546B (en)
BR (1) BR112013012693A2 (en)
ES (1) ES2525443T3 (en)
MY (1) MY161112A (en)
WO (1) WO2012069340A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9296896B2 (en) 2010-11-23 2016-03-29 Basf Se Polyamides with nanoparticles on the surface
DE102011084269A1 (en) * 2011-10-11 2013-04-11 Evonik Degussa Gmbh Process for the preparation of polymer nanoparticle compounds by means of a nanoparticle dispersion
CN103865008B (en) * 2014-03-28 2016-05-25 西南石油大学 Polyamide-amide hybridized nanometer silica dissaving polymer and preparation method thereof
DE102014214751A1 (en) 2014-07-28 2016-01-28 Leibniz-Institut Für Polymerforschung Dresden E.V. MODIFIED PLASTIC SURFACES AND METHOD FOR THEIR PRODUCTION
CN110240168B (en) * 2019-06-13 2021-01-08 浙江大学 Preparation method of small-size modified nano silicon dioxide

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2071250A (en) 1931-07-03 1937-02-16 Du Pont Linear condensation polymers
US2071251A (en) 1931-07-03 1937-02-16 Du Pont Fiber and method of producing it
US2130523A (en) 1935-01-02 1938-09-20 Du Pont Linear polyamides and their production
US2130948A (en) 1937-04-09 1938-09-20 Du Pont Synthetic fiber
US2241322A (en) 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides from cyclic amides
US2312966A (en) 1940-04-01 1943-03-02 Du Pont Polymeric material
US2512606A (en) 1945-09-12 1950-06-27 Du Pont Polyamides and method for obtaining same
IL24111A (en) 1964-08-24 1969-02-27 Du Pont Linear polyamides
NL7007122A (en) * 1970-05-15 1971-11-17 Treating plastics granules esp polyamidepolyester rapidly effected - by spraying them in a drying zone
US4144123A (en) 1974-07-19 1979-03-13 Basf Aktiengesellschaft Incorporating a crosslinked polyamidoamine condensation product into paper-making pulp
US4252844A (en) * 1978-07-26 1981-02-24 Union Carbide Corporation Process for mixing liquid additives with solid materials under sonic velocity conditions
DE2934854A1 (en) 1979-08-29 1981-09-10 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING NITROGEN-CONDENSING PRODUCTS AND THE USE THEREOF
NL8001764A (en) 1980-03-26 1981-10-16 Stamicarbon PREPARATION OF HIGH MOLECULAR POLYTRAMETHYLENE ADIPAMIDE.
NL8001762A (en) 1980-03-26 1981-10-16 Stamicarbon PREPARATION OF ARTICLES BASED ON POLYAMIDE.
NL8001763A (en) 1980-03-26 1981-10-16 Stamicarbon PREPARATION OF POLYTETRAMETHYLENE ADIPAMIDE.
DE3321579A1 (en) 1983-06-15 1984-12-20 Basf Ag, 6700 Ludwigshafen METHOD FOR THE CONTINUOUS PRODUCTION OF POLYAMIDES
DE3321581A1 (en) 1983-06-15 1984-12-20 Basf Ag, 6700 Ludwigshafen METHOD FOR THE CONTINUOUS PRODUCTION OF POLYAMIDES
EP0299444B2 (en) 1987-07-17 2007-02-14 BASF Aktiengesellschaft Partially aromatic polyamides with a reduced triamine content
US5308648A (en) * 1992-09-30 1994-05-03 Union Carbide Chemicals & Plastics Technology Corporation Spray application of plastics additives to polymers
DE4240110A1 (en) 1992-11-28 1994-06-01 Basf Ag Condensation products of polyalkylene polyamines, process for their preparation and their use in the manufacture of paper
DE4244194A1 (en) 1992-12-24 1994-06-30 Basf Ag Water-soluble condensation products from compounds containing amino groups and crosslinking agents, processes for their preparation and their use
DE4401055A1 (en) 1994-01-15 1995-07-20 Basf Ag Process for the preparation of thermoplastic polyesters with a low carboxyl end group content
BR9706970A (en) 1996-01-08 1999-04-06 Basf Ag Process for the preparation of condensates and adducts containing amino and use of high molecular weight polymeric fractions
DE19616120A1 (en) 1996-04-23 1997-10-30 Basf Ag Process for the preparation of finely divided water-insoluble polymers of aziridines, modified, water-insoluble polymers of aziridines and their use
DE19931720A1 (en) 1999-07-08 2001-01-11 Basf Ag Polymer hydrogel mixture, useful for the production of absorption materials, comprises a hydrogel forming polymer having acidic groups and a hydrogel forming polymer having amine and/or imine groups.
DE19921507A1 (en) 1999-05-10 2000-11-16 Basf Ag Process for the fractionation of water-soluble or dispersible amino group-containing polymers with a broad molar mass distribution
JP2002036267A (en) * 2000-07-26 2002-02-05 Taiyo Kagaku Kk Method for manufacturing thermosetting resin molded article utilizing waste product of pet resin
FR2851567B1 (en) 2003-02-24 2005-04-22 Solvay PROCESS FOR MANUFACTURING NANOCOMPOSITES
CN101040001B (en) 2004-10-18 2010-05-05 托帕斯高级聚合物有限公司 Polymer blends for producing films with a reduced number of defects
EP1969040B1 (en) * 2005-11-23 2012-07-25 Controlled Polymers A/S Method for producing coloured polymer granulate
WO2007074108A1 (en) * 2005-12-28 2007-07-05 Basf Se Process for production of a water-absorbing material
WO2008084021A1 (en) 2007-01-11 2008-07-17 Basf Se Process for making polymer nanocomposites
JP5535086B2 (en) * 2008-01-22 2014-07-02 ビーエーエスエフ ソシエタス・ヨーロピア Coated polyoxymethylene
JP2011515523A (en) 2008-03-18 2011-05-19 ビーエーエスエフ ソシエタス・ヨーロピア Polyamide-nanocomposite with hyperbranched polyethyleneimine
JP2011515522A (en) 2008-03-18 2011-05-19 ビーエーエスエフ ソシエタス・ヨーロピア Polyamide-nanocomposite with hyperbranched polyetheramine
MY156724A (en) 2008-11-11 2016-03-15 Basf Se Stabilized polyamides
EP2582742B1 (en) * 2010-06-18 2021-07-21 Dow Global Technologies LLC Coated polymeric particulates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
戈莱特利.人民卫生出版社.《感耦等离子体在原子光谱分析法中的应用》.人民卫生出版社,1992, *

Also Published As

Publication number Publication date
MY161112A (en) 2017-04-14
JP2013543921A (en) 2013-12-09
JP5795075B2 (en) 2015-10-14
EP2643390A1 (en) 2013-10-02
BR112013012693A2 (en) 2016-09-06
KR101905206B1 (en) 2018-10-05
ES2525443T3 (en) 2014-12-23
CN103328546A (en) 2013-09-25
WO2012069340A1 (en) 2012-05-31
KR20130129227A (en) 2013-11-27
EP2643390B1 (en) 2014-10-15

Similar Documents

Publication Publication Date Title
CN103328546B (en) Polyamide having nanoparticles on the surface
JP6558498B2 (en) Method for producing polyamide fine particles
US9296896B2 (en) Polyamides with nanoparticles on the surface
US10787559B2 (en) Powder comprising polymer-coated glass particles
KR101007531B1 (en) Process for preparing particles based on a thermoplastic polymer and powder thus obtained
Jin et al. Effect of surface modification on impact strength and flexural strength of poly (lactic acid)/silicon carbide nanocomposites
US20120181487A1 (en) Thermoplastic molding composition
SI1809691T1 (en) Polyester polymer and copolymer compositions containing titanium carbide particles
CN103304987A (en) Polyamide composition containing electrically conductive carbon
JP6168237B2 (en) Polybutylene terephthalate resin powder mixture for molding materials
JP2014503632A (en) Star and dendritic branched polymers with flame retardancy
KR100668571B1 (en) Polytrimethylene Terephthalate Composition Particles and Process for Producing the Same
JP2011037989A (en) Polyester container
JP6744912B2 (en) Method for reducing aldehyde content in polymeric materials
CN1332764A (en) Method of producing branched polyamides
CN113461918A (en) Synthetic method of polyester chip for low-extraction film
KR20060067884A (en) Composite porous fillers, method of preparation and use
CN104046025A (en) Thermoplastic Resine Composition Having Excellent Emi Shielding Property
CN112876860B (en) Biodegradable antistatic graphene in-situ polymerization copolyester cast film and preparation process thereof
JP5272511B2 (en) Method for producing polybutylene terephthalate
JP2019026670A (en) Polyamide composition and molding
CN1357021A (en) Amide-type polymer/silicon polymer blends and processes of making same
JP6526974B2 (en) Polyamide resin composition, molded article, and method for producing polyamide resin composition
CN114015043A (en) Method for preparing polyimide powder by chemical method
CN1302042C (en) Saturated polyester possessing excellent crystallization property

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20191205

Address after: 300 jiangxinsha Road, Pudong New Area, Shanghai

Patentee after: BASF AUX Y CHEMICALS CO., LTD.

Address before: Ludwigshafen, Germany

Patentee before: BASF European Company

TR01 Transfer of patent right